TW201300460A - Liquid crystal alignment agent, method for forming liquid crystal alignment film, liquid crystal display element and compound - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal alignment agent capable of providing an alignment defining force of liquid crystal molecule by optical-alignment method; while it is applied to VA type liquid crystal display element, a balance of vertical alignment defining force and coating property is excellent; while it is applied to TN type, STN type or transverse electric field mode liquid crystal display element, the alignment defining force is excellent. The said liquid crystal alignment agent comprises a radiation-sensitive polymer having a specific structure represented by the following formula (1'-1).

Description

Liquid crystal alignment agent, method for forming liquid crystal alignment film, liquid crystal display element and compound

The present invention relates to a liquid crystal alignment agent, a method of forming a liquid crystal alignment film, a liquid crystal display element, and a compound. More specifically, the present invention relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent alignment defining force of liquid crystal molecules, and a liquid crystal display element having excellent display quality.

It has been known that a nematic liquid crystal having positive dielectric anisotropy is formed into a sandwich structure by a substrate with a transparent electrode having a liquid crystal alignment film, and the long axis of the liquid crystal molecules is continuously continuous between the substrates as needed. A liquid crystal display element such as a TN (twisted nematic) type and an STN (super twisted nematic) type which are formed by twisting 0 to 360° (see Patent Documents 1 and 2).

In such a liquid crystal display device, in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the surface of the substrate in one direction by using a cloth such as rayon. However, when the liquid crystal alignment film is formed by the rubbing treatment, since dust or static electricity is easily generated in the step, dust adheres to the surface of the alignment film, which causes a problem of display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, there is a problem that the circuit of the TFT element is damaged due to the generated static electricity, which causes a decrease in yield. Further, in the liquid crystal display element which is becoming more and more refined in the future, as the density of the pixels is increased, irregularities are inevitably generated on the surface of the substrate, and thus it is increasingly difficult to perform uniform rubbing treatment.

Therefore, as another method of controlling the alignment of liquid crystal molecules in a liquid crystal display element, it is proposed to irradiate a photosensitive film such as polyvinyl cinnamate, polyimine, or azobenzene derivative formed on the surface of a substrate with a polarized or non-polarized film. A method of photoalignment that polarizes the radiation to impart a liquid crystal alignment capability. According to this method, static electricity or dust is not generated, and uniform liquid crystal alignment can be achieved (see Patent Documents 3 to 13).

On the other hand, as a mode of operation of a liquid crystal display element different from the above, a VA (Vertical Alignment) type liquid crystal display element in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is also known. In this operation mode, when a voltage is applied between the substrates so that the liquid crystal molecules tend to be parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward one direction in the substrate surface. As a method of realizing this, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a stripe on a transparent electrode, and a method of using liquid crystal molecules from a normal direction of a substrate toward a surface of a substrate by using a rubbing alignment film have been proposed. The method of slightly tilting the direction (pre-tilt), etc.

It is known that the above-described photoalignment method can also be effectively used as a method of controlling the tilt direction of liquid crystal molecules in a vertical alignment type liquid crystal display element. In other words, by using the liquid crystal alignment film which imparts the alignment control ability and the pretilt angle expression by the photo-alignment method, the tilt direction of the liquid crystal molecules when the voltage is applied can be uniformly controlled (see Patent Documents 11 to 12 and 14~). 16).

However, when a liquid crystal alignment film suitable for a TN type, an STN type, or a vertical alignment type liquid crystal display element is formed by a photo-alignment method, a liquid crystal alignment agent capable of stably exhibiting a liquid crystal alignment control force suitable for an industrial level has not been known. In particular, when it is used for a liquid crystal display element of a vertical alignment type, it should exhibit a liquid crystal alignment control force in a direction perpendicular to the substrate surface, and a polymer constituting the liquid crystal alignment film must have a straight liquid crystal structure, and thus it is contained. The coating property or printability of the liquid crystal alignment agent of the polymer is impaired, and a vertical alignment type liquid crystal alignment agent having good liquid crystal alignment property and good coating property has not been known until now.

However, in recent years, a liquid crystal display element of a lateral electric field mode (IPS mode) in which an electrode is formed only on one side of a pair of substrates disposed oppositely and an electric field is generated in a direction parallel to the substrate has been proposed (see Patent Document 17). ). The horizontal electric field type liquid crystal display element is an electrode in which an electrode is formed only on one side of a pair of substrates disposed opposite to each other, and an electric field type liquid crystal display element is formed in a direction parallel to the substrate, and electrodes are formed on the two substrates. In the conventional vertical electric field type liquid crystal display element which generates an electric field in the direction perpendicular to the substrate, it is known that it has a wide viewing angle characteristic and can perform high-quality display. In the liquid crystal display device of the horizontal electric field type, since the liquid crystal molecules respond to the electric field only in the direction parallel to the substrate, the problem of the refractive index change in the long-axis direction of the liquid crystal molecules does not occur, and the observer visually recognizes even when the viewing angle is changed. The contrast ratio and the change in the color of the display color are also small, so that high-quality display can be performed regardless of the angle of view.

However, when a liquid crystal alignment film suitable for such a horizontal electric field type liquid crystal display element is formed by a photo-alignment method, it has been pointed out that the alignment control force of liquid crystal molecules is insufficient, and thus improvement is required.

current technology

Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 56-91277

Patent Document 2 Japanese Patent Laid-Open No. Hei 1-120528

Patent Document 3 Japanese Patent Laid-Open No. Hei 6-287453

Patent Document 4 Japanese Patent Laid-Open No. Hei 10-251646

Patent Document 5 Japanese Patent Laid-Open No. 11-2815

Patent Document 6 Japanese Patent Laid-Open No. Hei 11-152475

Patent Document 7 Japanese Patent Laid-Open Publication No. 2000-144136

Patent Document 8 Japanese Patent Laid-Open Publication No. 2000-319510

Patent Document 9 Japanese Patent Laid-Open Publication No. 2000-281724

Patent Document 10 Japanese Patent Laid-Open No. Hei 9-297313

Patent Document 11 Japanese Patent Laid-Open Publication No. 2003-307736

Patent Document 12 Japanese Patent Laid-Open Publication No. 2004-163646

Patent Document 13 Japanese Patent Laid-Open Publication No. 2002-250924

Patent Document 14 Japanese Patent Laid-Open Publication No. 2004-83810

Patent Document 15 Japanese Patent Laid-Open No. Hei 9-211468

Patent Document 16 Japanese Patent Laid-Open Publication No. 2003-114437

Patent Document 17 US Patent No. 5,958,333

Patent Document 18 Japanese Patent Laid-Open Publication No. SHO 63-291922

Patent Document 19 Japanese Patent Laid-Open Publication No. 2010-097188

Non-patent literature

Non-Patent Document 1 "Science of Sol-Gel Method", issued by AGNE Chengfengshe (shares), 1988, pp. 154-161

The present invention has been made in view of the above circumstances, and an object thereof is to provide an alignment control force capable of imparting liquid crystal molecules by a photo-alignment method, and a vertical alignment control force and coating property when used for a vertical alignment type liquid crystal display element. On the other hand, when it is used for a liquid crystal display element of a TN type, an STN type, or a horizontal electric field type, it is a liquid crystal alignment agent of the liquid crystal alignment film which is excellent in the alignment control force.

Another object of the present invention is to provide a liquid crystal display element which is excellent in liquid crystal alignment control force and excellent in display quality.

Other objects and advantages of the invention will be apparent from the description which follows.

First, the above objects and advantages of the present invention are attained by a liquid crystal alignment agent containing at least one structure selected from the group consisting of structures represented by the following formulas (1') to (3') Radiation-sensitive polymer,

(In the formulae (1') to (3'), R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms or a fluoroalkyl group having 1 to 30 carbon atoms, or a steroid skeleton. a monovalent group, R ² is a cyclohexylene group or a phenyl group, and R ³ is a phenyl group or a group represented by the following formula (R ³ -1),

(In the formula (R ³ -1), X ¹ is ⁺ -COO- or ⁺ -OCO- or an oxygen atom (wherein the bond having "+" is bonded to the phenyl group), and d is 0 or 1, when When d is 0, e is an integer from 0 to 12. When d is 1, e is an integer from 1 to 12.

X is a single bond, an oxygen atom, a sulfur atom, a methylene group, an alkylene group having 2 or 3 carbon atoms, -CH=CH-, -NH-, *-COO- or *-OCO- (wherein There is a "*" transfer bond to R ² ), one of Z ¹ and Z ² is a carbonyl group, the other is a methylene or oxygen atom, a is an integer from 0 to 3, and b is 0 or 1. c is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ² and X existing may be the same or different. )

Secondly, the above objects and advantages of the present invention are attained by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention can form an alignment control force imparted to the liquid crystal molecules by the photo-alignment method, and is excellent in the balance of the vertical alignment control force and the coating property of the liquid crystal molecules when used for a vertical alignment type liquid crystal display element. On the other hand, when used for a liquid crystal display element of a TN type, an STN type, or a horizontal electric field type, the liquid crystal alignment film of the liquid crystal molecule is excellent in the alignment control force.

The liquid crystal display element of the present invention having such a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be used for various display devices because it can perform high-quality display and is inexpensive.

Form of implementing the invention

The liquid crystal alignment agent of the present invention contains a radiation-sensitive polymer having at least one group selected from the group consisting of the groups represented by the above formulas (1') to (3').

Examples of the skeleton of the above-mentioned radiation-sensitive polymer include polylysine, polyimine, polyphthalate, polyorganosiloxane, polyester, polyamine, cellulose and derivatives thereof, and polycondensation. Acetal, polystyrene and derivatives thereof, poly(styrene-phenylmaleimide) and derivatives thereof, poly(meth)acrylates and the like, among which polyorganosiloxanes are preferred. In other words, the radiation sensitive polymer contained in the liquid crystal alignment agent of the present invention preferably has at least one selected from the group consisting of groups represented by the above formulas (1') to (3'). A group of radiation sensitive polyorganosiloxanes.

<Inductive radioactive polyorganosiloxane>

The liquid crystal alignment agent of the present invention is preferably a radiation-sensitive polyorganosiloxane having at least one selected from the group consisting of groups represented by the above formulas (1') to (3'). Group.

Examples of the alkyl group having 1 to 30 carbon atoms of R ¹ in the above formulae (1') to (3') include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, and an octyl group. Indenyl, fluorenyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl And behenyl or the like; and as the fluoroalkyl group having 1 to 30 carbon atoms, for example, a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, a decafluorohexyl group, a pentafluoroheptyl group, The heptadecafluorooctyl group, the hexadecafluorodecyl group, etc., and a monovalent group having a steroid skeleton, for example, a 3-cholesteryl group or a 3-cholesteryl group can be mentioned. As the above alkyl group and fluoroalkyl group, a linear one is preferred.

When the R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, the liquid crystal alignment agent of the present invention can be preferably used for the TN type. a liquid crystal display element of the STN type or the transverse electric field type, and when R ¹ is an alkyl group having 2 to 30 carbon atoms or a fluoroalkyl group having 2 to 30 carbon atoms or a monovalent group having a steroid skeleton, The liquid crystal alignment agent of the present invention can be preferably used for a vertical alignment type liquid crystal display element.

The phenyl and exocyclohexyl groups of R ² are preferably a 1,4-phenylene group and a 1,4-cyclohexylene group, respectively.

The phenylene group of R ³ is preferably a 1,4-phenylene group, and when R ³ is a group represented by the above formula (R ³ -1), the phenylene group contained therein is preferably 1,4. - Stretch phenyl. e in the formula (R ³ -1) is preferably an integer of 0 to 4 when d is 0, and is preferably an integer of 1 to 4 when d is 1.

As X, a single bond or *-COO- is preferred (wherein a linkage with "*" is attached to R ² ).

Specific examples of the group of the radiation-sensitive polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention, the group represented by the above formula (1'), for example, the following formula (1'- 1)~(1'-36) each represented by a group;

The group represented by the above formula (2') may, for example, be a group represented by each of the following formulas (2'-1) to (2'-12);

The group represented by the above formula (3') is, for example, a group represented by each of the following formulas (3'-1) to (3'-6).

In the above examples, n is an integer from 0 to 20, and the group C _n H _2n+1 - may be substituted with one or more fluorine atoms.

The content ratio of at least one group selected from the group consisting of the groups represented by the above formulas (1') to (3') in the radiation-sensitive polyorganosiloxane containing the liquid crystal alignment agent of the present invention Preferably, it is from 0.2 to 6 millimoles per gram of polymer, more preferably from 0.3 to 5 millimoles per gram of polymer.

The radiation sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is at least one selected from the group consisting of groups represented by the above formulas (1') to (3'), It is preferred to further have an epoxy group. At this time, the epoxy equivalent of the radiation-sensitive polyorganosiloxane is preferably 150 g/mol or more, more preferably 200 to 10,000 g/mol, still more preferably 200 to 2000 g/mol. By using such an epoxy equivalent radiation-sensitive polyorganosiloxane, the liquid crystal alignment agent of the present invention does not impair the storage stability of the liquid crystal alignment agent, and can form a liquid crystal alignment property more excellently, and excellent afterimage characteristics. The liquid crystal alignment film is therefore preferred.

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography for the radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000. Very good for 3000~30000.

<Synthesis of Radiation-Specific Polyorganosiloxanes>

The radiation-sensitive polyorganosiloxane which is preferably contained in the liquid crystal alignment agent of the present invention can be synthesized by any method as described above. As a method of synthesizing the radiation-sensitive polyorganosiloxane which is contained in the liquid crystal alignment agent of the present invention, for example, a group having a group represented by each of the above formulas (1') to (3') can be employed. a method of hydrolyzing and condensing a hydrolyzable decane compound of at least one selected from the group, or a mixture of the hydrolyzable decane compound and another hydrolyzable decane compound; and a polyorganosiloxane having an epoxy group and a method of reacting at least one selected from the group consisting of the compounds represented by the formulas (1) to (3) (hereinafter referred to as "specific carboxylic acid"), and the like,

(R ¹ , R ² , R ³ , X, Z ¹ , Z ² , a, b, and c in the formulae (1) to (3) are respectively synonymous with the above formulas (1') to (3'). ).

Among them, the latter method is preferably used from the viewpoints of ease of synthesis of the raw material compound, ease of reaction, and the like.

Hereinafter, a preferred method for synthesizing the radiation-sensitive polyorganosiloxane containing the epoxy group in the liquid crystal alignment agent of the present invention, a method of reacting a polyorganosiloxane having an epoxy group with a specific carboxylic acid will be described.

[Polyorganosiloxane having an epoxy group]

The epoxy group in the polyorganosiloxane having an epoxy group is preferably an oxyethylene skeleton or a 1,2-epoxycycloalkane skeleton which is directly bonded to a ruthenium atom or can be interrupted by an oxygen atom therein. The epoxy group contained in the group in which an alkyl group is bonded to a halogen atom (a group having an epoxy group) is present in the polyorganosiloxane. The group having such an epoxy group may, for example, be a group represented by the following formula (EP-1) or (EP-2).

(In the formulas (EP-1) and (EP-2), "*" indicates a connection key.)

The epoxy equivalent of the polyorganosiloxane having an epoxy group is preferably from 100 to 10,000 g/mole, more preferably from 150 to 1000 g/mole.

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography on the polyorganosiloxane having an epoxy group is preferably from 500 to 100,000, more preferably from 1,000 to 10,000, particularly preferably from 1,000 to 5,000.

The polyorganosiloxane having an epoxy group can, for example, be a decane compound having an epoxy group or a decane compound having an epoxy group, preferably in the presence of a suitable organic solvent, water and a catalyst. A mixture of decane compounds is synthesized by hydrolysis and condensation.

The decane compound having an epoxy group may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidyloxypropane Methyldimethoxydecane, 3-glycidyloxypropylmethyldiethoxydecane, 3-glycidyloxypropyldimethylmethoxydecane, 3-glycidyloxy Propyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane Wait.

Examples of the other decane compound include tetrachloromethane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-second. Butoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri- or 2-butoxy decane, Fluorine trichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorotri-l-butoxy Decane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane, Methyl tri- or 2-butoxybutane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyl Triethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2-(trifluoromethyl)ethyl Tri-n-butoxy oxime Alkane, 2-(trifluoromethyl)ethyltri- or 2-butoxybutane, 2-(perfluoro-n-hexyl)ethyltrichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(Perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltri- or 2-butoxybutane, 2-(perfluoro-n-octyl)ethyltrichloromethane , 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxy Decane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-octyl)ethyltri - 2 - butyl decane, hydroxymethyl trichloro decane, hydroxymethyl trimethoxy decane, hydroxyethyl trimethoxy decane, hydroxymethyl tri-n-propoxy decane, hydroxymethyl triisopropoxy decane , hydroxymethyl tri-n-butoxy decane, hydroxymethyl tri- or 2-butoxy decane, 3-(methyl) propylene methoxy propyl trichloride Alkane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)acryloxypropyltricarboxylate N-propoxy decane, 3-(meth) propylene methoxypropyl triisopropoxy decane, 3-(methyl) propylene methoxy propyl tri-n-butoxy decane, 3-(methyl) Propylene methoxypropyl tri- or 2-butoxybutane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyl Tri-n-propoxy decane, 3-mercaptopropyltriisopropoxy decane, 3-mercaptopropyltri-n-butoxy decane, 3-mercaptopropyltri-di-butoxy decane, decylmethyltrimethoxy Base decane, decylmethyltriethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane , vinyl tri-n-butoxy decane, vinyl tri- or 2-butoxy decane, allyl trichloro decane, allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-butyl Propoxy decane, allylic Triisopropoxy decane, allyl tri-n-butoxy decane, allyl tri- or 2-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, Phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, phenyl tri-n-butoxy decane, phenyl tri- or 2-butoxy decane, methyl dichloro decane, methyl dimethoxy Decane, methyl diethoxy decane, methyl di-n-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di- or 2-butoxy decane, dimethyl Dichlorodecane, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldi-n-propoxydecane, dimethyldiisopropoxydecane, dimethyldi-n-butoxy Base decane, dimethyl di-?-butoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl) Ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl] N-propoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl]diisopropoxy decane, (a [2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-butoxybutane, (methyl) (3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropyl)diethoxydecane, (methyl) (3-mercaptopropyl)di-n-propoxyoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (methyl)(3-mercaptopropyl)di-n-butoxydecane, (methyl)(3-mercaptopropyl)di-butoxybutane, (methyl)(vinyl)dichlorodecane, (methyl)(vinyl)dimethoxydecane, (methyl) (vinyl)diethoxydecane, (meth)(vinyl)di-n-propoxydecane, (methyl)(vinyl)diisopropoxydecane, (methyl)(vinyl)di-n-butyl Butoxy decane, (methyl) (vinyl) di- or 2-butoxy decane, divinyl chlorin, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl Di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl di-di-butoxy decane, diphenyl dichloro decane, two Dimethoxy decane, diphenyl diethoxy decane, diphenyl di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl bis - 2 - butyloxydecane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, trimethyl chloro decane, trimethyl bromo decane, trimethyl iodonane, methoxy Trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, two-stage butoxy trimethyl decane , tertiary butoxy trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane a decane compound having one ruthenium atom such as (chloro)(methyl)diphenyl decane, (methoxy)(methyl)diphenyl decane or (ethoxy)(methyl)diphenyl decane, In addition, product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X can also be cited. -21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X -22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40 -2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247 , X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR -217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Electric Co., Ltd.) System); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray ‧ Dow Corning (share) system); FZ3711, FZ3722 (above, Japan UNICAR (shares) System); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51 , DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, CHISSO (manufactured by the company)); methyl decanoate MS51, methyl decanoate MS56 (above, Mitsubishi Chemical Corporation) ); ethyl citrate 28 Ethyl citrate 40, ethyl decanoate 48 (above, COLCOAT); partial condensate of GR100, GR650, GR908, GR950 (above, Showa Denko), and one of them can be used. the above.

As the other decane compound, among them, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene decyloxy group are preferably used. Propyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane,allyltrimethoxydecane,allyl Triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-mercaptopropyl triethoxy decane, decyl methyl trimethoxy decane And one or more selected from the group consisting of mercaptomethyltriethoxydecane, dimethyldimethoxydecane, and dimethyldiethoxydecane.

In the synthesis of the polyorganosiloxane having an epoxy group in the present invention, the use ratio of the decane compound having an epoxy group and other decane compounds is preferably adjusted so as to obtain an epoxy equivalent of the obtained polyorganosiloxane. The above preferred range is achieved.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon, a ketone, an ester, an ether, an alcohol, and the like.

Examples of the above-mentioned hydrocarbons include, for example, toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentanone, diethyl ketone, and cyclohexanone; and examples of the ester include, for example, the ester. Ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; as the ether, for example, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, tetrahydrofuran, two An alkane or the like; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol single N-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these, those which are not water-soluble are preferred.

These organic solvents can be used singly or in combination of two or more.

The amount of the organic solvent to be used is preferably 10 to 10,000 parts by weight, based on the total of 100 parts by weight of the decane compound (the total of the decane compound having an epoxy group and any other decane compound used arbitrarily). It is preferably 50 to 1000 parts by weight.

The amount of water used in the synthesis of the polyorganosiloxane having an epoxy group is preferably 1 to 30 moles, more preferably 1 to 30 moles per mole of the total amount of the decane compound.

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

The organic base may, for example, be ethylamine, diethylamine or piperazine. , organic primary or secondary amines such as piperidine, pyrrolidine, pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc. Organic tertiary amine; organic quaternary amine such as tetramethylammonium hydroxide. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; and organic quaternary amines such as tetramethylammonium hydroxide are preferred.

As a catalyst for synthesizing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, side reactions such as ring opening of an epoxy group are not generated, and a target polyorganosiloxane can be obtained at a high hydrolysis and condensation rate, so that production stability is excellent. Good. Further, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and a cinnamic acid derivative synthesized using an alkali metal compound or an organic base as a catalyst is extremely advantageous because it is extremely excellent in storage stability. The reason for this can be presumed to be that, as described in Non-Patent Document 1 ("Science of Sol-Gel Method", issued by AGNE Chengfengshe (share), 1988, pp. 154-161), alkali is used in hydrolysis and condensation reactions. When a metal compound or an organic base is used as a catalyst, whether a three-dimensional structure such as a random structure or a cage structure is formed, and a polyorganosiloxane having a small content of a sterol group can be obtained. In addition, since the sterol group content ratio is small, it is possible to suppress the condensation reaction between the sterol groups, and when the liquid crystal alignment agent of the present invention contains other polymers described later, it is also possible to suppress sterol groups. The condensation reaction with other polymers results in excellent storage stability.

As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used varies depending on the reaction conditions such as the type of the organic base and the temperature, and should be appropriately set, for example, 1 mol per mol of the decane compound, preferably 0.01 to 3 mol, more preferably 0.05~1 mole.

The hydrolysis and condensation reaction in the synthesis of a polyorganosiloxane having an epoxy group is preferably carried out by dissolving a decane compound having an epoxy group and other decane compounds as needed in an organic solvent, and the solution and the organic base, The water is mixed and heated by a suitable heating device such as an oil bath.

In the hydrolysis and condensation reaction, it is desirable that the heating temperature is preferably 130 ° C or lower, and more preferably 40 ° C to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. While heating, the mixture may be stirred or may not be stirred, or the mixture may be placed under reflux.

After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction mixture with water. In the case of this washing, washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like is preferred, and it is preferable to facilitate the washing operation. The washing is carried out until the aqueous layer after washing is neutral, and then the organic solvent layer is dried by using an appropriate desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed, whereby the desired polyorganoquinone having an epoxy group can be obtained. Oxytomane.

In the present invention, a commercially available product can be used as the polyorganosiloxane having an epoxy group. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (the above are manufactured by CHISSO Co., Ltd.).

[specific carboxylic acid]

Specific examples of the specific carboxylic acid include a carboxylic acid formed by linking a hydrogen atom to the linking bond of the group exemplified above as a group represented by each of the above formulas (1') to (3').

[Synthesis of Radiation-Specific Polyorganosiloxanes]

The liquid crystal alignment agent of the present invention preferably contains a radiation-sensitive polyorganosiloxane, and it is preferred to use a polyorganosiloxane having an epoxy group as described above and a specific carboxylic acid, preferably It can be easily obtained by reacting in the presence of a catalyst and an organic solvent.

Here, the specific carboxylic acid preferably has a total amount of 0.01 to 5 moles, more preferably 0.05 to 2 moles, more preferably the epoxy group 1 mole of the polyorganosiloxane. Good for 0.1 to 0.8 moles.

In the present invention, a compound represented by the following formula (4) may be used in place of a part of a specific carboxylic acid, within a range not impairing the effects of the present invention.

R ^I -R ^II -COOH (4)

(In the formula (4), R ^I is an alkyl group or alkoxy group having 8 to 20 carbon atoms or a fluoroalkyl group or a fluoroalkoxy group having 1 to 21 carbon atoms, and R ^II is a single bond, 1 , 4-cyclohexyl or 1,4-phenyl).

In this case, the synthesis of the radiation-sensitive polyorganosiloxane can be carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by the formula (4).

A preferred example of the compound represented by the above formula (4) is a compound represented by the following formula (4-1) or (4-2).

C _f F _2f+1 -C _g H _2g -COOH (4-1)

(In the above formula, f is an integer from 1 to 3, g is an integer from 3 to 18, h is an integer from 1 to 20, and i is an integer from 0 to 18.)

Among them, preferred are compounds represented by any one of the following formulae (4-2-1) to (4-2-3)

The compound represented by the above formula (4) is a compound which reacts with a polyorganosiloxane having an epoxy group to form a site which imparts a pretilt expression property to the obtained liquid crystal alignment film, and thus can be The liquid crystal alignment agent of the present invention is preferably used in the case of a vertical alignment type liquid crystal display device. In the present specification, the compound represented by the above formula (4) is hereinafter referred to as "other carboxylic acid".

In the present invention, when at least one selected from the group consisting of compounds represented by a specific carboxylic acid is used together with other carboxylic acids, the total use ratio of the specific carboxylic acid and the other carboxylic acid is relative to the polyorganosiloxane. The epoxy group has 1 mole, preferably 0.001 to 1.5 moles, more preferably 0.01 to 1 mole, still more preferably 0.05 to 0.9 moles. In this case, the total amount of the other carboxylic acid is preferably 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the carboxylic acid. When the use ratio of the other carboxylic acid exceeds 50 mol%, when the liquid crystal display element is turned on, there is a case where an abnormal region defect occurs.

As the catalyst, an organic base or a compound which is a so-called curing accelerator which promotes the reaction between an epoxy compound and an acid anhydride can be used.

The organic base may, for example, be ethylamine, diethylamine or piperazine. , organic primary or secondary amines such as piperidine, pyrrolidine, pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc. Organic tertiary amine; organic quaternary amine such as tetramethylammonium hydroxide.

Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; and organic quaternary amines such as tetramethylammonium hydroxide are preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2- Cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2 -Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate , 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitic acid Salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-three 2,4-Diamino-6-(2'-n-undecylimidazolyl)ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three , isocyanuric acid addition product of 2-methylimidazole, isocyanuric acid addition product of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')] Ethyl-s-three Imidazole compound such as isocyanuric acid adduct; organic phosphorus compound such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, Triphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate Salt, tetra-n-butyl fluorene, o,o-diethyldithiophosphate, tetra-n-butyl benzotriazole salt, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl fluorene tetraphenyl a quaternary phosphonium salt such as borate or tetraphenylphosphonium tetraphenylborate; a diazabicycloalkenyl such as 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof; Organometallic compounds such as zinc octoate, tin octylate, and aluminum acetonitrile acetate complex; tetra-ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc. Boron compound such as boron trifluoride or triphenyl borate; metal halide such as zinc chloride or tin chloride; high melting point such as amine amine addition accelerator such as diamine diamine or an amine and epoxy resin addition product; Dispersive latent curing accelerator; a microcapsule-type latent curing accelerator which coats the surface of a curing accelerator such as the above-mentioned imidazole compound, organophosphorus compound or quaternary phosphonium salt; amine salt type latent curing accelerator; Lewis acidate, Bronsted A latent curing accelerator such as a pyrolysis type thermal cationic polymerization type latent curing accelerator such as a salt acid salt.

Among these, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred.

The catalyst is preferably used in an amount of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polyorganosiloxane having an epoxy group.

The reaction of the polyorganosiloxane having an epoxy group with a specific carboxylic acid can be carried out in the presence of an organic solvent as needed. Examples of such an organic solvent include a hydrocarbon, an ether, an ester, a ketone, a decylamine, an alcohol, and the like. Among them, ethers, esters and ketones are preferred from the viewpoints of solubility of raw materials and products and easy purification of products. The solvent is preferably used in a ratio of a solid content concentration (the ratio of the weight of the component other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably 5 to 50% by weight.

The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours.

The synthesis of the radiation-sensitive polyorganosiloxane described above is carried out by the ring-opening addition of the epoxy group of the polyorganosiloxane having an epoxy group, and is introduced by the above formula (1')~( 3') A method of selecting at least one group selected from the group consisting of groups. This synthesis method is simple and is an extremely suitable method for increasing the introduction rate of at least one group selected from the group consisting of the groups represented by the above formulas (1') to (3').

<Other ingredients>

The liquid crystal alignment agent of the present invention contains the radiation sensitive polymer as described above, and is preferably a radiation sensitive polyorganosiloxane.

The liquid crystal alignment agent of the present invention may further contain other components in addition to the radiation sensitive polymer as described above, and preferably a radiation sensitive polyorganosiloxane, as long as the effects of the present invention are not impaired. Examples of such other components include polymers other than radiation-sensitive polymers (hereinafter referred to as "other polymers"), curing agents, curing catalysts, curing accelerators, and at least one epoxy group in the molecule. a compound (however, in addition to the above-mentioned radiation-sensitive polyorganosiloxane), hereinafter referred to as "epoxy compound".), a functional decane compound (however, in addition to the above-mentioned radiation-sensitive polyorganosiloxane) Alkane substances.), surfactants, etc.

[Other polymers]

The above other polymer can be used to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical characteristics of the obtained liquid crystal alignment film. The other polymer is a polymer which does not have any of the groups represented by the above formulas (1') to (3'), and is preferably, for example, polylysine or polyimine; a polyorganosiloxane (other than a "polyorganosiloxane"), other than a radioactive polyorganosiloxane. Polyurethane, polyester, polyamine, cellulose derivative, polycondensation An aldehyde, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like, and one or more of them can be used.

As the other polymer in the present invention, it is preferred to use at least one polymer or other polyorganosiloxane which is selected from the group consisting of polyproline and polyimine.

{polyglycine}

The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyglycolic acid of the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butane tetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dihydro- 3-furyl)-naphthalene [1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2 , 5-dioxa-3-furanyl)-naphthalene [1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione- 6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxaxotetrahydro 3-furanyl)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3. 0] octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraone, etc.; as aroma The tetracarboxylic dianhydride described in JP-A-2010-097188 (Patent Document 19) can be used, for example, in the case of the pyromellitic dianhydride.

As the tetracarboxylic dianhydride for synthesizing the aforementioned polyamic acid, it preferably contains an alicyclic tetracarboxylic dianhydride, and more preferably contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. At least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride.

As the tetracarboxylic dianhydride for synthesizing the polyamic acid, it is preferable to contain 10 mol% or more of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride with respect to all tetracarboxylic dianhydrides. At least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, more preferably 20 mol% or more, most preferably only 2,3,5-tricarboxyl ring At least one selected from the group consisting of pentyl acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

Examples of the diamine used for the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the aliphatic diamine include 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexa Methyldiamine or the like; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1,3-bis(amino group) Methyl)cyclohexane or the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl sulfide. , 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl) Benzene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-double (4-Aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylenedipropylene) bis(aniline), 4,4'-(m-phenylenediisopropylidene)bis(aniline), 1,4-bis(4-aminobenzene) Oxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminopurine , N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N' - bis(4-aminophenyl)benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis(4-aminobenzene) Base , 3,5-diaminobenzoic acid, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4 -diaminobenzene, cholesteneoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate , 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy) Cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzonitrileoxy) Cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1 - bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)- 4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane and the following formula (D- 1) the compound represented, etc.;

(In the formula (D-1), X ^I is an alkyl group having 1 to 3 carbon atoms, *-O-, *-COO- or *-OCO- (wherein a linkage bond with "*" and two Aminophenyl linkage.), m is 0 or 1, n is an integer from 0 to 2, and p is an integer from 1 to 20.

For example, 1,3-bis(3-aminopropyl)-tetramethyldicyclohexane or the like can be used as the diamine-based organic decane, and in addition to the above, it is also possible to use JP-A-2010-097188. The diamine described in the publication (Patent Document 19).

X ^I in the above formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, *-O- or *-COO- (wherein a linkage bond with a "*" and a diamine group) Phenyl linkage.). Specific examples of the group C _p H _2p+1 - group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-decyl group. , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nine Alkyl, n-icosyl, and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position and the 3,5-position relative to other groups.

Specific examples of the compound represented by the above formula (D-1) include, for example, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, and ten Pentameryl-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy- 2,5-Diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-di Aminobenzene, a compound represented by the following formula (D-1-1) to (D-1-4), and the like.

In the above formula (D-1), it is preferred that m and n are not 0 at the same time.

These diamines may be used singly or in combination of two or more.

The ratio of use of the tetracarboxylic dianhydride and the diamine provided in the polyaminic acid synthesis reaction is preferably 1 equivalent to the amine group contained in the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 The ratio of the equivalent is more preferably a ratio of 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of -20 to 150 ° C, more preferably 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably It is 2~10 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. Aprotic polar solvents such as N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by weight based on the total amount (a+b) of the reaction solution, and more preferably It is an amount of 5 to 30% by weight.

As described above, a reaction solution formed by dissolving polylysine can be obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be prepared by separating the polyamic acid contained in the reaction solution and then supplying the liquid crystal alignment agent, or may further purify the separated polyamic acid. Modulation of liquid crystal alignment agent.

When polypyridic acid is dehydrated and closed to form polyimine, the above reaction solution may be directly supplied to the dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated and supplied to the dehydration ring-closing reaction, or may be separated. The polylysine is purified and then supplied to a dehydration ring closure reaction.

The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure or by using an evaporator to distill off the organic solvent in the reaction solution. The method of the solvent or the like is carried out. Further, the polylysine can be dissolved again in an organic solvent, followed by precipitation with a poor solvent, or polylysine can be dissolved again in an organic solvent, and the resulting solution can be washed again. The poly-proline acid is purified by a method such as a step of distilling off the organic solvent in the solution by using an evaporator under reduced pressure.

{polyimine}

The polyimine can be synthesized by dehydrating and ring-closing the structure of the proline contained in the polyamic acid obtained as described above. At this time, the entire proline structure can be dehydrated and closed to be completely imidized, or only a part of the proline structure can be dehydrated and closed to form a partial ruthenium imide of a proline structure and a quinone structure. .

The dehydration ring closure of polylysine can be carried out by (i) heating the poly-proline, or (ii) dissolving the poly-proline in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. And it is carried out according to the method of heating, etc. as needed.

The reaction temperature in the above (i) method of heating the polyamic acid is preferably 50 to 200 ° C, and more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine decreases. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the poly-proline in the above (ii), the dehydrating agent may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is preferably used in an amount of from 0.01 to 20 mols per mol of the polyamic acid structural unit. Further, examples of the dehydration ring-closure catalyst include tertiary amines such as pyridine, collidine, lutidine, and triethylamine. However, it is not limited to this. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 to 10 mols based on 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring-closure reaction may be the same organic solvent as the organic solvent exemplified as the solvent used in the synthesis of the polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, and more preferably 1 to 8 hours.

The polyimine obtained in the above method (i) can be directly supplied to a liquid crystal alignment agent, or the obtained polyimine can be purified and then supplied to a liquid crystal alignment agent. On the other hand, in the method (ii), a reaction solution containing polyienimine can be obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after the dehydration agent and the dehydration ring closure catalyst are removed from the reaction solution, and the polyimine may be separated and then supplied to the liquid crystal alignment. The preparation of the agent may be carried out by refining the separated polyimine and then supplying it to the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and a method such as solvent replacement can be used. The separation and purification of the polyimine can be carried out by the same operation as the above separation and purification method as polylysine.

{Other polyorganosiloxanes}

The other polyorganosiloxane in the present invention is a polyorganosiloxane such as the above-mentioned radiation-sensitive polyorganosiloxane. Such other polyorganosiloxanes can, for example, be at least one decane selected from the group consisting of alkoxy decane and a halogenated decane compound, preferably in a suitable organic solvent in the presence of water and a catalyst. The compound (hereinafter also referred to as "raw material decane compound") is synthesized by hydrolysis and condensation.

The starting decane compound used herein may, for example, be tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane or tetra-di- butyl. Oxydecane, tetra-tertiary butoxydecane, tetrachlorodecane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, Methyl tri-n-butoxy decane, methyl tri- or 2-butoxy decane, methyl tri-tertiary butoxy decane, methyl triphenyloxy decane, methyl trichloro decane, ethyl trimethoxy Decane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri-butoxybutane, ethyl Tri-tertiary butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl dimethoxy decane, dimethyl di Oxydecane, dimethyldichlorodecane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, etc., and preferably used One or more of them are particularly preferably used from tetramethoxydecane, tetraethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, and phenyltriethoxylate. At least one selected from the group consisting of decane, dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane, and trimethylethoxydecane.

The other polyorganosiloxane in the present invention can be synthesized in the same manner as the above-described method for synthesizing a polyorganosiloxane having an epoxy group, in addition to the above-mentioned starting decane compound.

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography for other polyorganosiloxanes is preferably from 1,000 to 100,000, more preferably from 5,000 to 50,000.

{Use ratio of other polymers}

When the liquid crystal alignment agent of the present invention contains the radiation sensitive polymer and other polymers, the ratio of use of the other polymer is preferably 10,000 parts by weight or less based on 100 parts by weight of the radiation sensitive polymer. A more preferable use ratio of the other polymer differs depending on the kind of the polymer contained in the liquid crystal alignment agent of the present invention.

When the liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane and a group consisting of poly-proline and polyimine, the ratio of use of the two is relatively The total amount of the polyamic acid and the polyimine is 100 to 5000 parts by weight, and more preferably 200 to 2000 parts by weight, based on 100 parts by weight of the radiation-sensitive polyorganosiloxane.

On the other hand, when the liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane and other polyorganosiloxanes, the ratio of use of the two is relatively higher than that of the radiation-sensitive polyorganosiloxane. The amount of other polyorganosiloxane is 100 to 2000 parts by weight.

When the liquid crystal alignment agent of the present invention contains a radiation sensitive polymer and other polymers, as the other polymer species, at least one polymer selected from the group consisting of polyglycine and polyamidiamine is preferred. Or other polyorganosiloxane or both.

[curing agent and curing catalyst]

In order to make the radiation-sensitive polymer, preferably, the cross-linking reaction of the radiation-sensitive polyorganosiloxane is more robust, the above-mentioned curing agent and curing catalyst can be contained in the liquid crystal alignment agent of the present invention, and in order to promote the control of the curing agent The curing reaction can include the above-described curing accelerator in the liquid crystal alignment agent of the present invention.

As the curing agent, a curing agent which is generally used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, and examples thereof include a polyamine, a polycarboxylic acid anhydride, and a polybasic compound. Carboxylic acid, etc.

The polyvalent carboxylic acid anhydride may, for example, be an anhydride of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride.

Specific examples of the cyclohexane tricarboxylic anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and cyclohexane-1,3,5-tricarboxylic acid-3. 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrofuran anhydride, nadic anhydride, and twelve. a carbenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula (CA-1), and a tetracarboxylic dianhydride generally used in the synthesis of polylysine,

(In the formula (CA-1), q is an integer from 1 to 20.)

In addition, examples thereof include a Diels Alder reaction product of a conjugated double bond-containing alicyclic compound such as α-terpinene or an allo-olene, and a hydride of such a hydride. .

Examples of the curing catalyst include a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, and aluminum triacetate acetate. These catalysts are capable of catalyzing the cationic polymerization of epoxy groups produced via heating.

Examples of the curing accelerator include an imidazole compound, a quaternary phosphorus compound, and a quaternary amine compound; for example, 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof Azabicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, aluminum acetonitrile acetate complex; boron compounds such as boron trifluoride, triphenyl borate; such as zinc chloride, tin chloride a metal halide; a high melting point dispersion type latent curing accelerator such as a diamine diamine, an amine addition accelerator of an amine and an epoxy resin; and a surface coated with a polymer such as a quaternary phosphonium salt A capsule type latent curing accelerator; an amine salt type latent curing accelerator; a pyrolysis type thermal cationic polymerization type latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt.

[epoxy compound]

The epoxy compound can be contained in the liquid crystal alignment agent of the present invention from the viewpoint of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate.

Examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-four Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N - diglycidyl-aminomethylcyclohexane or the like is preferred.

When the liquid crystal alignment agent of the present invention contains an epoxy compound, the content thereof is 100 parts by weight or less, more preferably 40 parts by weight or less, more preferably 0.1% by weight based on the total of the above-mentioned radiation sensitive polymer and any other polymer used arbitrarily. 30 parts by weight.

Further, when the liquid crystal alignment agent of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination in order to effectively produce a crosslinking reaction.

[functional decane compound]

In order to improve the adhesiveness of the obtained liquid crystal alignment film and a board|substrate, the said functional decane compound can be used. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-hydrazinopropyltrimethoxydecane, 3-mercaptopropylpropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxyl Carbonyl-3-aminopropyltriethoxydecane, N-triethoxycarbenylpropyltriethylamine, N-trimethoxycarbamidopropyltriethylamine, 10 -trimethoxycarbamido-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamidinyl -3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Baseline, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Base decane, N-di (oxygen) Ethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane And a tetracarboxylic dianhydride as described in the patent document 18 (JP-A-63-291922). A reactant or the like with a decane compound having an amine group.

When the liquid crystal aligning agent of the present invention contains a functional decane compound, the content ratio thereof is preferably 50 parts by weight or less based on 100 parts by weight of the total of the radiation sensitive polymer and any other polymer used arbitrarily. More preferably, it is 20 parts by weight or less.

[Surfactant]

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a polyalkylene oxide surfactant, and a fluorine-containing interfacial activity. Agents, etc.

When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the total of the liquid crystal alignment agent.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains a radiation sensitive polymer as an essential component as described above, and if necessary, contains other components as needed, and is preferably a solution-like composition in which each component is dissolved in an organic solvent. modulation.

As the organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, a solvent which dissolves the radiation-sensitive polymer and other components which are used arbitrarily, and which does not react with these, is preferable.

The organic solvent which can be preferably used for the liquid crystal alignment agent of the present invention differs depending on the type of the polymer contained in the liquid crystal alignment agent of the present invention.

When the liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane and at least one polymer selected from the group consisting of polyglycolic acid and polyamidimide, and in addition to containing a radiation-sensitive polyorganoindene At least one polymer selected from the group consisting of polyamine and polyamidene, and a preferred organic solvent in the case of other polyorganooxane, which can be used as a polylysine synthesis An organic solvent exemplified as the solvent. These organic solvents may be used singly or in combination of two or more.

On the other hand, when the liquid crystal alignment agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or contains a radiation-sensitive polyorganosiloxane and other polyorganosiloxane, it does not contain poly A preferred organic solvent in the case of at least one selected from the group consisting of lysine and polyamidiamine may, for example, be 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol. Monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, C Cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, acetic acid N-butyl ester, isobutyl acetate, butyl acetate, n-amyl acetate, diethyl amyl acetate, 3-methyl acetate Butyl ketone, methyl amyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate Ester and the like. Among them, preferred are n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, and diethyl amyl acetate.

A preferred solvent which can be used for preparing the liquid crystal alignment agent of the present invention can be obtained by using one or a combination of two or more kinds of the above organic solvents depending on the presence or absence of other polymers and the type of the polymer, and is preferably as described below. In the solid content concentration, the components contained in the liquid crystal alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is in the range of 25 mN/m to 40 mN/m.

The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent, is selected in consideration of viscosity, volatility, etc., and is preferably 1 ~10% by weight. The liquid crystal alignment agent of the present invention is coated on the surface of the substrate to form a coating film constituting the liquid crystal alignment film, and when the solid content concentration is less than 1% by weight, it is difficult to obtain a good liquid crystal alignment because the film thickness of the coating film is too small. The condition of the membrane. On the other hand, when the solid content concentration exceeds 10% by weight, the coating film thickness is too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to cause insufficient coating properties. The range of the particularly preferable solid content concentration differs depending on the method used for coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, it is particularly preferably from 1.5 to 4.5% by weight. When the printing method is employed, the solid content concentration is particularly preferably in the range of 3 to 9% by weight, whereby the solution viscosity is in the range of 12 to 50 mPa‧s. When the inkjet method is employed, the solid content concentration is particularly preferably in the range of 1 to 5% by weight, whereby the solution viscosity is in the range of 3 to 15 mPa‧s.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

<Method of Forming Liquid Crystal Alignment Film>

The liquid crystal alignment agent of the present invention can be preferably used for a liquid crystal display element which can be used for a TN type, an STN type, a lateral electric field type (IPS type) or a VA type by a photo-alignment method. When the liquid crystal display element of the present invention is used for a liquid crystal display device of a TN type, an STN type or a lateral electric field type, particularly when used in a liquid crystal display element of a lateral electric field type, the effect of the present invention can be maximized. It is better.

In order to form a liquid crystal alignment film by using the liquid crystal alignment agent of the present invention, a method of forming a coating film by applying the liquid crystal alignment agent of the present invention onto a substrate and irradiating the coating film with radiation may be employed.

When the liquid crystal alignment agent of the present invention is used for a liquid crystal display device of a TN type, an STN type or a VA type, first, two substrates each having a patterned transparent conductive film are provided as a pair, and each of them is transparent. The liquid crystal alignment agent of the present invention is applied onto the conductive film forming surface to form a coating film. On the other hand, when the liquid crystal alignment agent of the present invention is used for a liquid crystal display device of a horizontal electric field type, a substrate having an electrode having a transparent conductive film or a metal film patterned on one surface and an electrode not provided with an electrode The substrate is used as a pair, and the liquid crystal alignment agent of the present invention is applied to the surface of the comb-shaped electrode and the surface of the counter substrate, respectively, to form a coating film.

In either case, as the substrate, for example, glass such as float glass or soda lime glass, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, or polycarbonate can be used. A transparent substrate formed of a plastic substrate such as an ester. As the transparent conductive film, for example, an ITO film formed of In ₂ O ₃ —SnO ₂ , a NESA (registered trademark) film formed of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. The formation pattern of the transparent conductive film and the metal film can be, for example, a method of performing photolithography after forming a transparent conductive film without a pattern, a method of forming a pattern by a sputtering method, or the like, and a desired use in forming a transparent conductive film. The method of patterning the mask, etc.

When the liquid crystal alignment agent is applied onto the substrate, a functional decane compound, titanate or the like may be applied to the substrate and the electrode in advance in order to further improve the adhesion between the substrate or the conductive film or the electrode and the coating film.

The method of applying a liquid crystal alignment agent to a substrate is preferably carried out by an appropriate coating method such as an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method, followed by preheating the coated surface (prebaking) And then baking (post-baking) to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and post-baking conditions, preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and preferably 5 to 200. Minutes, preferably 10 to 100 minutes. The film thickness after the post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

The liquid crystal alignment ability is imparted by irradiating the coating film thus formed with linearly polarized light or partially polarized radiation or non-polarized radiation. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, and irradiation may be performed from the oblique direction in order to impart a pretilt angle. Further, these may be combined. get on. When irradiating radiation of unpolarized light, the direction of irradiation must be an oblique direction.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength region can be obtained by using the above-described light source in combination with a method such as a filter or a diffraction grating.

The irradiation amount of radiation, preferably 1J / m ² or more and not to 10000J / m ^2, more preferably 10 ~ 3000J / m ^2. In addition, when a liquid crystal alignment ability is imparted to a coating film formed of a conventional liquid crystal alignment agent by a photo-alignment method, a radiation irradiation amount of 10,000 J/m ² or more is required. And when the liquid crystal alignment agent of the present invention, the irradiation amount of radiation when even if the optical alignment method of 3000J / m ² or less, and further 1000J / m ² or less, it is possible to impart good liquid crystal to capacity with, and contribute to the liquid crystal display Productivity improvement of components and reduction in manufacturing costs.

<Method of Manufacturing Liquid Crystal Display Element>

The liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, as follows.

First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a structure in which liquid crystal is sandwiched between the pair of substrates is manufactured. For the production of the liquid crystal cell, for example, the following two methods can be cited.

The first method is a previously known method. First, the two substrates are disposed opposite to each other with a gap (cell gap) therebetween, and the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded together. After the filled liquid crystal is injected into the divided cell gap, the injection hole is closed, whereby the liquid crystal cell can be manufactured.

As a second method, it is called a method of ODF (One Drop Fill). Wherein, for example, an ultraviolet curable sealing material is applied to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and then the liquid crystal is dropped on the liquid crystal alignment film surface, and then the other substrate is bonded to make the liquid crystal alignment film relatively Then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby the liquid crystal cell can be produced.

Whichever method is employed, it is desirable to heat the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase, and then slowly cool to room temperature, thereby removing the flow alignment when the liquid crystal is filled.

Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization directions of the linearly polarized light radiation irradiated on the two substrates forming the liquid crystal alignment film and the angle between each of the substrates and the polarizing plate.

The sealing agent may, for example, be an epoxy resin containing an alumina ball as a separator and a curing agent.

Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. A liquid crystal having positive dielectric anisotropy for forming a nematic liquid crystal is preferable, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl ring can be used. An alkane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. Further, in the liquid crystal, for example, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate can be further added; as the trade names "C-15" and "CB-15" (above) A chiral agent sold by MERCK Co., Ltd.; a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate.

The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate formed by sandwiching a polarizing film with a cellulose acetate protective film or a polarizing plate formed by the H film itself, and the polarizing film is formed by stretching and aligning polyvinyl alcohol. The result of absorbing iodine is called "H film".

In the liquid crystal display device of the present invention thus produced, since the liquid crystal molecules have excellent alignment control power, the display characteristics are excellent.

Example

Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples.

The weight average molecular weight Mw in the following synthesis examples is a polystyrene-converted value measured by gel permeation chromatography under the following conditions.

Column: Tosoh (stock) system, TSKgel GRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

Further, in the following synthesis examples, the synthesis of the raw material compound and the polymer is repeated as needed according to the following synthesis route, thereby ensuring the necessary amount in the following examples.

<Synthesis Example of Polyorganooxane having an Epoxy Group>

Synthesis example ES1

In a reaction vessel with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 10.0 g were added. Triethylamine and mix at room temperature.

Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then mixed under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to give an epoxy group as a viscous transparent liquid. Polyorganosiloxane (ES-1).

By ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, it was found that an epoxy group-based peak having the same theoretical strength was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm, whereby the reaction was confirmed. A side reaction in which no epoxy group is produced.

The viscosity, Mw and epoxy equivalent of the epoxy group-containing polyorganosiloxane (ES-1) are shown in Table 1.

Synthesis example ES2~3

The polyorganosiloxane (ES-2) and (ES-3) having an epoxy group as a viscous transparent liquid were obtained in the same manner as in Synthesis Example 1, except that the raw materials to be added were as shown in Table 1.

The Mw and epoxy equivalents of these epoxy group-containing polyorganosiloxanes are shown in Table 1.

In addition, in Table 1, the abbreviation of a raw material decane compound has the following meaning respectively.

ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

MTMS: methyltrimethoxydecane

PTMS: Phenyltrimethoxydecane

<Synthesis Example of Specific Carboxylic Acid>

Compounds (3-1), (3-2) and (3-3) were separately prepared according to the following Scheme 1.

Synthetic route 1

In the above Scheme 1, the product when R is a hydrogen atom is the compound (3-1), the product when R is a fluorine atom is the compound (3-2), and when R is a cyclohexyl group. The resultant is the compound (3-3).

The following synthesis operations were carried out in an inert gas atmosphere.

Synthesis example (3)-1

In a 3 L three-necked flask equipped with a condenser tube and a dropping funnel, a 40% by weight ethanol solution (corresponding to 0.88 molebenzyltrimethylammonium hydroxide) of 0.39 moles and tetramethylammonium hydroxide was added and heated to 40 ° C. A 50% by weight aqueous solution of glyoxylic acid (corresponding to 0.59 molamic acid) was added dropwise thereto, and the mixture was stirred at 50 ° C for 1 hour to carry out a reaction. After the end of the reaction, 700 mL of pure water and 1 L of toluene were added to the reaction mixture, and 1 N sulfuric acid was further added to adjust the pH of the aqueous layer to about 2. Then, after raising the temperature to 70 ° C and stirring well, the organic layer was taken out and washed with water. The organic layer was subjected to several extraction operations using a mixed aqueous solution (pH about 8) formed of a 1 N aqueous ammonium chloride solution and 1 N aqueous ammonia. The obtained aqueous layer was combined, and 1,2-dichloroethane was added thereto, and 1N hydrochloric acid was further added thereto to adjust the pH of the aqueous phase to about 2, followed by shaking. The organic layer was taken out, the solvent was distilled off, and the obtained solid was recrystallized from toluene to obtain 26.9 g of Compound (3-1).

Synthesis Examples (3)-2 and (3)-3

In addition to the above-mentioned Synthesis Example (3)-1, 0.39 mol of 5-fluoroindole (synthesis example (3)-2) and 5-cyclohexylfluorene (synthesis example (3)-3) were used instead of hydrazine, respectively, and Synthesis Example (3)-1 was carried out in the same manner, and 33 g of the compound (3-2) and 29 g of the compound (3-3) were respectively obtained.

<Comparative Synthesis Example of Carboxylic Acid>

Synthesis Example R-1

The comparative carboxylic acid (R-1) was synthesized according to the following Scheme 2.

Synthetic route 2

In a 200 mL three-necked flask, 11.21 g of 4-hydroxychalcone, 8.35 g of ethyl bromoacetate, 13.8 g of potassium carbonate and 100 mL of dimethylacetamide were added, and the mixture was stirred at 120 ° C for 7 hours to carry out a reaction. After the reaction was completed, the reaction solution was cooled to room temperature, and then 100 mL of ethyl acetate was added. After the organic layer was washed with water, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixed solution of ethanol and water (ethanol: water = 4:1 (volume ratio)) to obtain 11.4 g. Compound (R-1a).

Next, 6.2 g of the above compound (R-1a), 2 g of sodium hydroxide, 200 mL of ethanol, and 50 mL of water were placed in a 500 mL three-necked flask having a condenser, and the mixture was stirred under reflux for 3 hours to carry out a reaction. After completion of the reaction, the reaction mixture was cooled, and then diluted with hydrochloric acid to make it acidic. Then, 500 mL of ethyl acetate was added to carry out liquid separation. After the obtained organic layer was washed with water, the solvent was removed under reduced pressure to give Compound (R-1).

<Synthesis Example of Radiation-Tensible Polyorganooxane>

Synthesis Example S-1

Into a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane (ES-1) having an epoxy group obtained in the above Synthesis Example ES-1, 26 g of methyl isobutyl ketone, and 4.30 g of the above synthesis example (3) were added. The compound (3-1) obtained in -1 and 0.10 g of UCAT 18X (trade name, quaternary ammonium salt of San-Apro Co., Ltd.) were stirred at 80 ° C for 12 hours to carry out a reaction. After the completion of the reaction, methanol was added to the reaction mixture, and the resulting precipitate was recovered, dissolved in ethyl acetate, and the resulting solution was washed three times with water, and then the solvent was evaporated to give 9 g of a radiation-sensitive polyorganic compound as a white powder. Oxane (S-1). The radiation-sensitive linear polyorganosiloxane (S-1) had a weight average molecular weight Mw of 5,500.

Synthesis Examples S-2 and S-3

In addition to the above-mentioned Synthesis Example S-1, the kind and amount of the polyorganosiloxane having an epoxy group and the carboxylic acid (the compound represented by the above formula (3)) were respectively as described in Table 2, and In the same manner as in Synthesis Example S-1, the radiation-sensitive polyorganosiloxanes (S-2) and (S-3) were obtained, respectively. The weight average molecular weights Mw of these sensitizing radiopolyorganosiloxanes are shown in Table 2.

<Comparative Synthesis Example of Radiation-Tensible Polyorganooxane>

Synthesis Example RS-1

In the same manner as in Synthesis Example S-1, except that the compound (R-1) obtained in the above Synthesis Example R-1 was used instead of the compound (3-1) in the above Synthesis Example S-1, a radiation-induced linear polymerization was obtained. Organic decane (RS-1). The weight average molecular weight Mw of the radiation-sensitive linear polyorganosiloxane (RS-1) is shown in Table 2.

<Synthesis Example of Other Polymers>

[Synthesis Example of Polylysine]

Synthesis Example PA-1

19.61 g (0.1 mol) of cyclobutane tetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2,2'-dimethylbiphenyl were dissolved in 367.6 g of N- The reaction was carried out for 6 hours at room temperature in methyl-2-pyrrolidone. Next, the reaction mixture was poured into a very large amount of methanol to precipitate a reaction product. The precipitate was recovered, washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 35 g of polyamine (PA-1).

Synthesis Example PA-2

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g (0.1 mol) of cyclohexane bis(methylamine) were dissolved in 329.3 g of N-methyl-2. In the pyrrolidone, the reaction was carried out at 60 ° C for 6 hours. Next, the reaction mixture was poured into a very large amount of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of polyamine (PA-2).

A part of the polyamine acid (PA-2) was supplied to the liquid crystal alignment agent in the examples described later, and the remainder was supplied to the synthesis of the following polyimine.

[Synthesis of Polyimine]

Synthesis example PI-1

17.5 g of the polylysine (PA-2) obtained in the above Synthesis Example PA-2 was added, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto at 120 ° C. The ruthenium imidization reaction was carried out for 4 hours. The resulting reaction mixture was poured into a very large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to give 15 g of polyimine (PI-1).

Example 1

<Modulation of liquid crystal alignment agent>

100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in the above Example S-1 and 1000 parts by weight of the poly-proline (PA) obtained in the above Synthesis Example PA-1 as another polymer -1), dissolved in a mixed solvent formed of N-methyl-2-pyrrolidone and butyl cellosolve (N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio)) In the middle, a solution having a solid concentration of 3.0% by weight was formed. The solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent.

<Manufacture of liquid crystal display element>

Applying the liquid crystal alignment agent prepared above to an electrode forming surface of a glass substrate having a chrome-plated metal electrode patterned in a comb shape by using a spin coater, and a surface of the opposite glass substrate on which the electrode is not provided, and It was prebaked on a hot plate at 80 ° C for 1 minute, and then baked in an oven which was subjected to nitrogen substitution in a tank, and baked at 200 ° C for 1 hour to form a coating film having a film thickness of 0.1 μm. Next, using a Hg-Xe lamp and a Glan Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet rays having a wavelength of 313 nm at 600 J/m ² from the normal direction of the substrate to obtain a pair of substrates having a liquid crystal alignment film.

By screen printing, the outer periphery of the surface on which the liquid crystal alignment film is formed on the substrate having the chromium metal electrode in the pair of substrates, and an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied, and then a pair is applied. The liquid crystal alignment film of the substrate faced, pressed, and the substrates were irradiated with ultraviolet rays in opposite directions, and heated at 150 ° C for 1 hour to thermally cure the adhesive. Next, liquid crystal MLC-7028 manufactured by MERCK Co., Ltd. was filled in the gap of the substrate from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. Next, a polarizing plate is bonded to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and orthogonal to the projection direction of the ultraviolet light axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a liquid crystal display of a horizontal electric field type element.

<Evaluation of Liquid Crystal Display Element>

The liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 3.

(1) Evaluation of liquid crystal alignment

An abnormal region where there is no change in brightness when the voltage of 5 V was applied to the liquid crystal display element manufactured as described above was observed by an optical microscope, and when the abnormal region was not observed, the liquid crystal alignment property was evaluated as "good". When an abnormal region was observed, the liquid crystal alignment property was evaluated as "not good".

(2) Evaluation of voltage retention rate

With respect to the liquid crystal display element manufactured above, a voltage of 5 V was applied at 60 ° C for an application time of 60 μsec and an interval of 167 msec, and then the voltage holding ratio from the release of the application to 167 msec was measured. For the measurement device, the company (manufactured by TOYO Corporation, VHR-1) was used.

Examples 2 to 8 and Comparative Example 1

A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the type of the radiation-sensitive polyorganosiloxane and the kind and amount of other polymers were changed as described in Table 1, respectively, and a liquid crystal display element was produced. Conduct an evaluation. The evaluation results are shown in Table 3.

Further, in Comparative Example 1, the amount of polarized ultraviolet light irradiation when the liquid crystal display element was produced was 1000 J/m ² .

Claims (11)

A liquid crystal alignment agent comprising a radiation sensitive polymer having at least one selected from the group consisting of structures represented by the following formulas (1') to (3') structure, In the formulae (1') to (3'), R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, or 1 having a steroid skeleton. a valence group, R ² is a cyclohexylene group or a phenyl group, and R ³ is a phenyl group or a group represented by the following formula (R ³ -1), In the formula (R ³ -1), X ¹ is a ⁺ -COO- or a ⁺ -OCO- or an oxygen atom (wherein a bond having a "+" is bonded to a phenyl group), and d is 0 or 1, when d When 0, e is an integer from 0 to 12. When d is 1, e is an integer from 1 to 12, and X is a single bond, an oxygen atom, a sulfur atom, a methylene group, and a carbon number of 2 or 3. An alkyl group, -CH=CH-, -NH-, *-COO- or *-OCO- (wherein the linkage with "*" is bonded to R ² ), one of Z ¹ and Z ² is a carbonyl group The other is a methylene group or an oxygen atom, a is an integer of 0 to 3, b is 0 or 1, and c is an integer of 0 to 3, wherein when a is 2 or 3, a plurality of R ² are present. And X can be the same or different. The liquid crystal alignment agent of claim 1, wherein the radiation sensitive polymer is at least one structure selected from the group consisting of structures represented by the formulas (1') to (3') Radiation-sensitive polyorganosiloxane. The liquid crystal alignment agent of claim 2, wherein the radiation-sensitive polyorganosiloxane is a polyorganosiloxane having an epoxy group and is represented by each of the following formulas (1) to (3). a reaction product of at least one compound selected from the group consisting of compounds, R ¹ , R ² , R ³ , X, Z ¹ , Z ² , a, b and c in the formulae (1) to (3) are synonymous with the formulae (1') to (3'), respectively. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising at least one polymer selected from the group consisting of polylysine and polyimine, but the polymer does not contain Any of the structures represented by the formulas (1') to (3'). The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising a polyorganosiloxane, wherein the polyorganosiloxane does not contain the respective formulas (1') to (3') Any of the structures shown. A method for forming a liquid crystal alignment film, comprising the step of forming a coating film by applying a liquid crystal alignment agent according to any one of claims 1 to 5 on a substrate, and irradiating the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5. The liquid crystal display device of claim 7, wherein the group R ¹ in the formula (1') to (3') is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or a carbon atom. The number is 1 to 5 fluoroalkyl groups, and the liquid crystal display element is a liquid crystal display element of a TN type, an STN type, or a lateral electric field type. The liquid crystal display element of claim 8, wherein the liquid crystal display element is a liquid crystal display element of a horizontal electric field type. The liquid crystal display device of claim 7, wherein the group R ¹ in the formula (1') to (3') is an alkyl group having 5 to 30 carbon atoms or a carbon number of 5 to 30. A fluoroalkyl group, or a monovalent group having a steroid skeleton, and the liquid crystal display element is a vertically aligned liquid crystal display element. a compound represented by any one of the following formulas (1) to (3), In the formulae (1) to (3), R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, or a monovalent group having a steroid skeleton. a group, R ² is a cyclohexylene group or a phenyl group, and R ³ is a phenyl group or a group represented by the following formula (R ³ -1), In the formula (R ³ -1), X ¹ is a ⁺ -COO- or a ⁺ -OCO- or an oxygen atom (wherein a bond having a "+" is bonded to a phenyl group), and d is 0 or 1, when d When 0, e is an integer from 0 to 12. When d is 1, e is an integer from 1 to 12, and X is a single bond, an oxygen atom, a sulfur atom, a methylene group, and a carbon number of 2 or 3. An alkyl group, -CH=CH-, -NH-, *-COO- or *-OCO- (wherein the linkage with "*" is bonded to R ² ), one of Z ¹ and Z ² is a carbonyl group The other is a methylene group or an oxygen atom, a is an integer of 0 to 3, b is 0 or 1, c is an integer of 0 to 3, and when a is 2 or 3, a plurality of R ² and X can be the same or different.